JP5014797B2 - Method of operating a compression ignition internal combustion engine combined with a catalytic reformer - Google Patents

Abstract

A process for operating a compression ignition internal combustion engine in combination with a catalytic partial oxidation reformer and, optionally, an exhaust gas aftertreater, wherein: (a) a mixture of a first fuel and air, wherein the first fuel comprises Fischer-Tropsch derived fuel, is introduced in the combustion chamber of the engine; (b) exhaust gas is discharged from the engine and optionally partly recirculated to the combustion chamber of the engine; (c) a second fuel and oxygen and/or steam are supplied to the catalytic partial oxidation reformer to produce synthesis gas, wherein the second fuel comprises Fischer-Tropsch derived fuel; (d) at least part of the synthesis gas is supplied to: (i) the exhaust gas aftertreater; (ii) the combustion chamber of the engine; or to both.

Description

The present invention relates to a method for operating a compression ignition internal combustion engine in combination with a catalytic reformer.

BACKGROUND OF THE INVENTION The demand for automobile exhaust emissions is becoming increasingly demanding. For this reason, aftertreatment systems for exhaust gases of internal combustion engines have been developed.

Spark ignition internal combustion engines can be operated at or near stoichiometric fuel / air conditions. It is common to treat engine (engine) exhaust gas operated at stoichiometric amounts with a three-way conversion catalyst that promotes oxidation of unburned hydrocarbons and carbon monoxide and reduction of nitrogen oxides (NO _x ).

To reduce particulate emissions and improve efficiency, compression ignition internal combustion engines are typically operated at lean fuel / air conditions. Since the presence of oxygen interferes with the reduction of NO _x, lean exhaust gas can not be processed in a three-way conversion catalyst. When the fuel injection timing is advanced from the top dead center to reduce the amount, the amount of NO _x released can be reduced, but the granular emission increases. Increasing the fuel injection advance has the opposite effect and is often a “trade” between NO _x and particulate emissions.

To reduce the _the NO _x releasing amount of lean-burn internal combustion engine, NO _x reducing exhaust gas treatment systems have been developed. Such NO _x reduction systems typically contain a NO _x reduction catalyst.

For example, US 5,412,946 describes a NO _x reduction catalyst having Pt on zeolite. Such a catalyst promotes the reduction of NO _x to nitrogen in the presence of a reducing compound. Conventionally, it has been described that hydrocarbons, hydrogen, or synthesis gas is used as a reducing compound for this type of NO _x reduction catalyst.

Also known in the prior art are NO _x reduction systems comprising both deNO _x catalyst and NO _x solvent, for example from US 5,874,057, US 5,473,887 and WO 01/34950. During the lean operation, NO _x is absorbed from the exhaust gas, and during the rich operation, the solvent is regenerated and the catalyst promotes the reduction of NO _x to nitrogen. By adding fuel, hydrogen or synthesis gas to the lean exhaust gas, the exhaust gas can be periodically rich (low oxygen).

  An alternative method of reducing the emissions of a compression ignition internal combustion engine is by a method conventionally known as fumigation. In the fumigation method, gaseous fuel is mixed with engine intake air before introducing the air / gaseous fuel mixture into the engine cylinder. Both diesel fuel and air / gaseous fuel mixture are introduced into the engine. Known fumigating gaseous fuels are, for example, natural gas, liquefied petroleum gas (LPG) and hydrogen gas.

Other methods of emissions, in particular to reduce the NO _x is by exhaust gas recirculation (EGR). According enhance recirculation of the exhaust gas, NO _x emissions are reduced. However, high levels of recirculation can reduce combustion. Conventionally, various methods for enriching the recirculated exhaust gas have been reported. For example, L.M. K. S Teo et al., “Hydrogen and Biodiesel Mixtures as Fuels for the Compressed Engine and the Fuel in the Fuel”. Is described.

In order to guarantee future emission limits, particularly for lean combustion compression ignition internal combustion engines, there is a need to further reduce emissions, particularly nitrogen oxide emissions.
US 5,412,946 US 5,874,057 US 5,473,887 WO 01/34950 GB-B-2077289 EP-A-0147873 EP-A-0583836 US-A-4125556 US-A-4478955 WO 99/19249 L. K. S Teo et al., “Hydrogen and Biodiesel Mixtures as Fuels for the Compression Ignite Engine” Proceedings of the THEISEL 2002 Fuel Chemistry Division Reprints 2002, 47 (2), 502 R. H. Clark et al., “The Environmental Benefits of Shell GTL Diesel”, Proceedings of the 4th Int. Fuels Colloquim, January 15-16, 2003, Tech. Akad. Esslingen, Germany

SUMMARY OF THE INVENTION In a compression ignition internal combustion engine, a fuel containing a Fischer-Tropsch derived hydrocarbon stream as a fuel for the engine for advanced exhaust gas aftertreatment and / or advanced combustion engine operation. • It has now been found that emissions can be further reduced when used in combination with synthesis gas derived from Tropsch fuel-containing fuels.

  The invention therefore relates to a method for operating a compression ignition internal combustion engine in combination with a catalytic partial oxidation reformer according to claim 1.

BRIEF DESCRIPTION OF THE DRAWINGS Different embodiments of the invention are described in detail by way of example with reference to the schematic FIGS.
Figure 1 illustrates a present invention method for supplying syngas NO _x removal system.
FIG. 2 shows the method according to the invention for supplying synthesis gas to the combustion chamber of the engine.

FIG. 3 shows the method according to the invention in which the synthesis gas is fed into the combustion chamber of the engine together with the recirculated exhaust gas.
FIG. 4 illustrates the inventive method of supplying synthesis gas to both the NO _x removal system and the solid oxide fuel cell.

DETAILED DESCRIPTION OF THE INVENTION In the method of the present invention, a compression ignition internal combustion engine is operated in combination with a catalytic partial oxidation reformer. Here, the catalytic partial oxidation reformer is a catalytic reaction zone for steam reforming, autothermal reforming or partial oxidation of hydrocarbon fuels to form a gas mixture containing synthesis gas, for example hydrogen and carbon oxides. Say that. These reactions are conventionally described in more detail, for example, in Fuel Chemistry Division Reprints 2002, 47 (2), 502.

The reformer produces synthesis gas that is used to operate the compression ignition internal combustion engine in a manner that reduces emissions. Both the first fuel, the engine fuel and the second fuel, the reformer fuel, contain Fischer-Tropsch derived fuel. “Fischer-Tropsch induction” means that the fuel is a synthetic product or derivative of the Fischer-Tropsch condensation process. The Fischer-Tropsch reaction converts carbon monoxide and hydrogen to long chain, usually paraffinic hydrocarbons, usually at elevated temperature and / or pressure, in the presence of a suitable catalyst.
n (CO + 2H ₂ ) = (— CH ₂ —) _n + nH ₂ O + heat

  The fuel can be obtained directly from a Fischer-Tropsch reaction or indirectly, for example, by fractionation of a Fischer-Tropsch synthesis product or indirectly from a hydrotreated Fischer-Tropsch synthesis product. Hydrogenation can be performed by hydrocracking to adjust the boiling point range (see, for example, GB-B-2077289 and EP-A-0147873) and / or hydrogen whose temperature flow characteristics can be improved by increasing the proportion of branched-chain paraffins. Isomerization can be included. In EP-A-0583836, a Fischer-Tropsch synthesis product is first subjected to hydroconversion under conditions that do not substantially undergo isomerization or hydrocracking (hydrogenation of olefin components and oxygen-containing components). And then hydrotreating at least a portion of the resulting product under conditions such that hydrocracking and isomerization occurs to produce a substantially paraffinic hydrocarbon fuel. The law is described. The desired fuel fraction may subsequently be isolated, for example by distillation.

  In order to improve the properties of the Fischer-Tropsch condensation product, polymerization, alkylation, distillation, cracking-decarboxylation, isomerization and hydrogenation, for example as described in US Pat. No. 4,125,566 and US Pat. No. 4,478,955 Other post-synthesis treatments such as modification may be employed.

  The engine and reformer preferably use the same fuel, i.e. the first fuel and the second fuel are the same fuel. Using the same fuel has the advantage that only one fuel storage tank is required to supply fuel to both the engine and the reformer.

The use of Fischer-Tropsch derived fuel in a compression ignition internal combustion engine provides several advantages. These fuels are highly paraffinic and therefore have a high cetane number. Also, the sulfur content is low, thereby reducing the risk of sulfur poisoning to the catalyst system. Moreover, these fuels are inherently clean and therefore emit less particles (soot), NO _x , hydrocarbons and carbon monoxide. In this regard, R.A. H. Clark et al., “The Environmental Benefits of Shell GTL Diesel”, Proceedings of the 4th Int. Fuels Colloquim, January 15-16, 2003, Tech. Akad. See Esslingen, Germany.

  For example, from WO 99/19249, it is known that Fischer-Tropsch derived fuels are very suitable for catalytic reformers. The advantage of Fischer-Tropsch derived fuels over conventional internal combustion fuels is cleanliness (no sulfur and less soot formation).

  To benefit from these characteristics, both the first fuel and the second fuel are preferably at least 10% (v / v) Fischer-Tropsch derived fuel, more preferably at least 50% (v / v), More preferably it contains at least 80% (v / v) or even more preferably consists of a Fischer-Tropsch derived fuel. It will be appreciated that the first fuel itself must be suitable for a compression ignition internal combustion engine. Thus, the primary fuel must meet the requirements for this type of engine fuel, such as standards for cetane number, flash point, total aromatic content, total sulfur content, fuel distillation curve and cold flow. Accordingly, the non-Fischer-Tropsch derived fuel portion of the primary fuel is preferably a petroleum derived gas oil, optionally combined with an oxygenate such as an alcohol or fatty acid methyl ester and a conventional diesel fuel additive. Diesel base fuel. It has been found that if part of the fuel is a Fischer-Tropsch derived fuel, then the fuel for the compression ignition internal combustion engine will require less additive. This means that if the first fuel and the second fuel are the same, the reformer is also supplied with fuel with less additive than conventional diesel fuel. This is advantageous because some diesel fuel additives can adversely affect catalyst stability.

The Fischer-Tropsch derived fuel is preferably a gas oil, ie a fraction having a boiling point in the boiling range of the gas oil.
In the method of the present invention, engine exhaust emissions are further reduced by using synthesis gas to improve aftertreatment and / or engine operation. Such further reduction can be achieved by supplying a synthesis gas exhaust gas treatment device, for example, NO _x removal system, and / or to the combustion chamber of the engine.

  Syngas is produced in a catalytic partial oxidation reformer. The reaction occurring in the reformer may be steam reforming, partial oxidation, autothermal reforming or a combination thereof. Suitable catalysts and reaction conditions for such reformers are known in the art. The fuel is reacted with water (steam reforming), oxygen (partial oxidation) or both (autothermal reforming or partial oxidation). Since this reaction does not require an external heat source for maintaining the reaction, partial oxidation or autothermal reforming is preferred.

  Air is usually used as the oxygen source of the reformer. Alternatively, engine exhaust gas may be used as an oxygen and / or water vapor source. Therefore, if exhaust gas is used as the steam source of the reformer, water may be condensed from the exhaust gas even if the exhaust gas is introduced into the reformer or before the exhaust gas is introduced into the reformer. .

In one aspect of the present invention, the exhaust gas of the engine (i.e., without re-circulated to the combustion chamber of the engine, also part of the exhaust gas is not supplied to the reformer) is supplied to the NO _x removal system. At least a portion of the generated synthesis gas is also supplied to the NO _x removal system.

The NO _x removal system preferably comprises a NO _x trap comprising a NO _x reduction catalyst and a NO _x solvent. Such NO _x trap is conventionally known, for example WO 01/34950 and US 5,473,887. A general example of a suitable NO _x trap is a combination of platinum on an alumina support as a catalyst and barium oxide as a solvent. In one embodiment of the invention, the NO _x removal system has a single NO _x trap. With continuously feeding the exhaust gas to the NO _x trap, intermittently supplying the synthesis gas. If the trap contains a BaO solvent, NO _x is absorbed by the solvent as, for example, Ba (NO ₃ ) ₂ while only exhaust gas is supplied to the NO _x trap. While supplying exhaust gas and synthesis gas to the NO _x trap, the trap is regenerated and the catalyst promotes the reduction of NO _x to nitrogen.

In another embodiment of the present invention, the NO _x removal system comprises two NO _x traps as described above. The two traps are operated in a so-called swing manner. On one of the trap to supply exhaust gas, the other trap supplying synthesis gas, the NO _x is reduced to nitrogen desorption (regeneration mode), and becomes the opposite. Therefore, exhaust gas and synthesis gas are alternately supplied to each trap. The advantage of this swing-type operation is that regeneration is performed in the absence of oxygen compared to the single trap operation described above, and thus more efficient regeneration is possible.

A particular advantage by using Fischer-Tropsch derived fuel in both the engine and reformer is that the fuel does not contain sulfur and therefore has a low sulfur oxide content in the exhaust and synthesis gases. Sulfur oxides are strongly adsorbed on NO _x traps and can adversely affect the performance of such traps.

In another embodiment, the NO _x removal system includes a NO _x reduction catalyst but no NO _x solvent. Such NO _x removal systems are known in the art. Usually, such a system is constructed by supporting platinum on zeolite. Exhaust gas and synthesis gas are simultaneously supplied to the catalyst. The catalyst promotes the reduction of NO _x to nitrogen and the synthesis gas acts as a reducing agent.

  In the second aspect of the present invention, at least part of the synthesis gas is supplied to the combustion chamber of the engine. In one embodiment (fumigation), the synthesis gas is mixed with intake air and supplied to the combustion chamber prior to introducing air into the combustion chamber. In another embodiment (abundant EGR), synthesis gas is added to the recirculated exhaust gas and fed to the combustion chamber along with it.

  In fumigation embodiments, the concentration of synthesis gas in the intake air stream may need to be below the flammability limit. Furthermore, it will be appreciated that care should be taken to optimize the overall fuel to air ratio (where fuel is defined as the first fuel supplied to the combustion chamber + syngas). The amount of synthesis gas supplied to the combustion chamber of the engine is such that the volume ratio of “syngas” to “first fuel” supplied to the combustion chamber is preferably 25% or less, more preferably 20% or less. It is.

When syngas and recirculated exhaust gas are supplied to the combustion chamber together (abundant EGR), the volume ratio of “syngas + exhaust gas combination” to “first fuel” supplied to the combustion chamber is preferred Is 25% or less. The combination of synthesis gas and exhaust gas is usually introduced into the combustion chamber from a special valve.
When a portion of the synthesis gas is introduced into the combustion chamber (fumigation or abundant EGR), it may be combined with a synthesis gas assisted post-treatment such as the aforementioned synthesis gas assisted NO _x removal.

  In the method of the present invention, at least a part of the generated synthesis gas is used for the progress of aftertreatment or the progress of engine operation. Further, a part of the synthesis gas may be supplied for power generation of the fuel cell. This method can provide an on-vehicle power generation vehicle. The electricity thus obtained can be used, for example, for the development of auxiliary power for air pacing or valve control. The fuel cell is preferably a solid oxide fuel cell.

  The present invention will be described with reference to FIGS. Flow control means, heat exchangers and other means for process control are not shown.

FIG. 1 shows a method of operating a compression ignition internal combustion engine 1 in combination with a catalytic partial oxidation reformer 2 and a NO _x removal system 3. Here, the synthesis gas is supplied to the NO _x removal system 3. Fuel (Fischer-Tropsch derived gas oil) and air in the fuel storage tank 4 are supplied to the engine 1 via lines 5 and 6, respectively. The fuel is vaporized, and the vaporized fuel and air are mixed before combustion in a combustion chamber (not shown) of the engine 1. Exhaust gas is discharged from the engine 1 via the line 7. The catalytic partial oxidation reformer 2 has a catalyst bed for partial oxidation. Fuel and air in the storage tank 4 are supplied to the reformer 2 via lines 8 and 9, respectively. The synthesis gas is produced by the reformer 2 and discharged via the line 10. The NO _x removal system 3 has two NO _x traps 11 and 12. The NO _x trap 11, line 13 from the line 7, the exhaust gas is supplied via valve 14. The synthesis gas is supplied to the NO _x trap 12 from the line 10 through the line 15 and the valve 16. When the amount of NO _x absorbed on the NO _x trap 11 exceeds a specific limit, when the synthesis gas is supplied to the trap via the line 17 and the valve 18, the trap 11 is regenerated. During regeneration of the NO _x trap 11, exhaust gas is supplied to the NO _x trap 12 via the line 19 and the valve 20, and NO _x is absorbed. The treated exhaust gas is discharged from the NO _x removal system 3 via the line 21.

  FIG. 2 shows a method of operating the compression ignition internal combustion engine 1 combined with the contact partial oxidation reformer 2. Here, the synthesis gas is supplied to the combustion chamber of the engine 1. The synthesis gas discharged from the reformer 2 via the line 10 is added to the intake air of the engine 1.

  FIG. 3 shows a method of operating the compression ignition internal combustion engine 1 combined with the contact partial oxidation reformer 2. Here, the synthesis gas and the recirculated exhaust gas are supplied to the combustion chamber of the engine 1 together. A part of the exhaust gas discharged from the engine 1 via the line 7 is recirculated to the combustion chamber of the engine 1 via the line 22. The synthesis gas discharged from the reformer 2 via the line 10 is added to the recirculated exhaust gas in the line 22.

FIG. 4 shows a method of operating the compression ignition internal combustion engine 1 in combination with the catalytic partial oxidation reformer 2 and the NO _x removal system 3. Here, a part of the synthesis gas is supplied to the NO _x removal system 3, and a part of the synthesis gas is supplied to the solid oxide fuel cell 23. In this embodiment, only a portion of the synthesis gas discharged from the reformer 2 via the line 10 is supplied to the NO _x removal system 3 via the line 24. The remainder of the synthesis gas is guided to the anode 25 of the fuel cell 23 via the line 26. Air is guided to the cathode 27 of the fuel cell 23 via a line 28. A reaction occurs between the anode and the cathode of the fuel cell 23 to generate electricity. The exhaust gas from the fuel cell is discharged from the fuel cell via line 29.

Illustration of the present invention method in the case of supplying the synthesis gas in the NO _x removal system. Explanatory drawing of this invention method in the case of supplying synthesis gas to the combustion chamber of an engine. Explanatory drawing of the method of this invention in the case of supplying synthesis gas to the combustion chamber of an engine with the exhaust gas which recirculated. Illustration of the present invention method in the case of supplying the synthesis gas to both of the NO _x removal system and solid oxide fuel cells.

Explanation of symbols

1 Compression ignition internal combustion engine (engine)
2 catalytic partial oxidation reformer 3 NO _x removal system 4 fuel storage tank 5 fuel line 6 air line 7 exhaust gas line 8 fuel line 9 air line 10 syngas line 11 NO _x trap 12 NO _x trap 13 exhaust gas line 15 synthesis Gas line 17 synthesis gas line 19 exhaust gas line 21 treated exhaust gas 22 recirculation exhaust gas line 23 solid oxide fuel cell 24 synthesis gas line 26 synthesis gas line 25 anode 27 cathode 28 air line 29 exhaust gas line

Claims (9)

(A) introducing a mixture of a first fuel containing Fischer-Tropsch derived fuel and air into a combustion chamber of a compression ignition internal combustion engine;
(B) exhausting the exhaust gas from the engine and recirculating at least a portion thereof to the combustion chamber of the engine;
(C) supplying a second fuel containing Fischer-Tropsch derived fuel and oxygen and / or steam to the catalytic partial oxidation reformer to produce synthesis gas;
(D) supplying at least a portion of the synthesis gas to (i) an exhaust gas aftertreatment device, or (ii) a combustion chamber of an engine, or both;
Including
A non-recirculating portion of the exhaust gas and at least a portion of the synthesis gas are fed to a NO _x removal system comprising a NO _x trap comprising a NO _x reduction catalyst and a NO _x solvent ;
A portion of the synthesis gas is supplied to the combustion chamber along with the recirculated exhaust gas,
The first fuel and the second fuel comprise at least 10% (v / v) Fischer-Tropsch derived fuel;
Operation of catalytic partial oxidation reformer and NO _x removal system and any combination of the compression ignition internal combustion engine as an exhaust gas aftertreatment device.   The method of claim 1, wherein the first fuel and the second fuel are the same fuel. 3. The method of claim 1 or 2, wherein the first fuel and the second fuel comprise at least 50% (v / v) Fischer-Tropsch derived fuel.   The method according to any one of claims 1 to 3, wherein the Fischer-Tropsch derived fuel is a gas oil. The method according to claim 1, wherein the non-recirculating part of the exhaust gas is continuously supplied to the NO _x trap and the synthesis gas is supplied intermittently to the NO _x trap. A non-recirculating portion of the exhaust gas in turn to each trap so that the NO _x removal system has two NO _x traps, one trap being supplied with exhaust gas and the other trap being supplied with synthesis gas And the process according to any one of claims 1 to 4 , wherein a synthesis gas is supplied. The supply amount of the synthesis gas into the combustion chamber of the engine, according to claim 1 to 6 volume ratio of "syngas" versus "first fuel" to be supplied to the combustion chamber is in an amount such that 25% or less The method according to any one of the above. The amount of synthesis gas supplied to the combustion chamber and the amount of exhaust gas recirculated to the combustion chamber is 25% of the volume ratio of “combination of synthesis gas + exhaust gas” to “first fuel” supplied to the combustion chamber. The method according to any one of claims 1 to 7, wherein the amount is as follows. For power generation method according to any one of claims 1 to 8, a portion of the synthesis gas is supplied to the fuel cells.